Refining of liquid or semiliquid carbonaceous materials



Patented Dec. 30,1952

REFININ G OF LIQUID R SEMILIQUID CARBONACEOU S MATERIALS Gerald E. Phillips, Cranford, N. J., assignor to Standard Oil Development Company, a corporation of Delaware No Drawing. Application August 31, 1949,

' Serial No. 113,470

iciaims. (01.196-56) This invention relates to an improved method of treating or refining liquid or semi-liquid carbonaceous materials such as shale oil or petroleum residuum and particularly to processes which give improved yields of distillate oil.

Shale oil and heavy petroleum residuum have been subjected to pyrolytic treatments in order to increase the amount of distillate oil obtained therefrom. These processes, commonly termed coking, involve heating the petroleum residuum, shale oil or the like to temperatures of 700 to about 1100 F. and maintaining them at these temperatures until they are converted to gaseous material, liquid distillate fractions and solid coke. Since the gaseous material and coke are of limited usefulness or of less value than the distillate oils, it is obviously of advantage to so conduct the pyrolytic treatment of the shale oil or petroleum residuum asto obtain a maximum amount of distillate oil.

It is the object of this invention to provide the art with a novel method of treating shale oil or heavy petroleum residuum to increase the amount of distillate oil obtained therefrom.

It is also the object of this invention t provide the art with a method of pyrolytically treating or coking shale oil or heavy petroleum residuum which increases the yield of distillate oil primarily at the expense of coke formation.

These and other objects will appear more clear- 1y from the detailed specification and claims which follow.

It has now been found that an improvement in liquid yields or distillate oils can be obtained by coking shale oil or petroleum residuum in the presence of spent shale fines.

The exact mechanism by which the shale fines eifect this improvement in yield is not known but would appear to be catalytic in nature since an increase in liquid yield is not obtained when sand, an inert solid is substituted for the shale fines in the coking process. The catalytic efiect of the shale fines in this coking. operation is quite surprising since such fines do not appear to exert any appreciable eiiect in the cracking of ordinary gas oil. Moreover, other materials which have a catalytic effect in the cracking ofgas oil have a detrimental elfect upon the yield of distillate oil when used in the coking of shale oil or petroleum residuum. V p

The liquid to semi-liquid carbonaceous materials which can be advantageously coked in accordance with the present invention includes the i. e., those portions boiling above 700 F. and petroleum residues obtained after subjecting petro leum crude oil to atmospheric or vacuum distillation to remove therefrom a major portionof the constituents which boil below about 800 to 900 F. at atmospheric pressure. The petroleum'residues ordinarily comprise at most about20 to 30 vol. of the original oil and will have a boiling range above about 800 to 900 F.

The shale fines which may be utilizedas catalysts in the coking operation inaccordance with with the present invention may conveniently be the fines resulting from attrition'of spent shale in the retorting or distillation of oil shal by the fluidized solidstechnique. .The fines ordinarily represent from 30 to of the spent shale and a representative size distribution of thevspent -shale fines is as follows:

Particle size: Percent 7 Less than 10 microns 30-40 10-20 microns 30-40 20-40 microns 10-15 40+ microns 5-10 While particles of this size are desirable and conveniently obtained it Will be understood that larger sized particles can also be used and that shale fines of any desired size can be obtained by grinding the spent shale. Such spent shale may contain up to around 10 to 12% of burnable carbonaceous material. The fines used in the coking operation in accordance with the present invention are recoverable for reuse in the coking operation by burnin the coke or carbonaceous material that is deposited thereon during the coking operationf The amount of spent shale fines used may vary between about 2 to about 20, preferably from 5 to 15 pounds of fines per gallon of oil charged. Coking temperatures, are ordinarily between about 700 to 1100 F., preferably from 950 to 1050 F. and are maintained until the distillate oil is driven off and the residue is converted to coke.

The following examples are illustrative. of the present invention. l

EXAMPLE 1 spent Coloradoshale fines per gallon of shale oil.

The following table presents yield and inspection data from these operations.

aeaaees Table I The mechanism of the improved yield of liquid products due to the employment of spent shale Bage firg andhstleani clokingiof fines appears to be catalytic in nature in that an 00150 see 01 L111 er atmospheric con (11 6 inc ease in l quid yield 18 not obtainedwhen sand. Colorado Maximum en t m r an inert solid, as well as other materials such as shale oil 519 sil ca gel and bauxite which are noncatalytic for E33 cracking of hydrocarbons is substituted for the tempting o# +io#/ shale fines in the coking process.

without as? $23? fi fi f fl g w EXAMPLE 3 l es 95 Since the eiTect of spent shale fines upon the coking of liquid to semi-liquid carbonaceous ma- Y'ld,w'ht nt [1 B 11 magic: page terials appeared to be catalytic in nature two Dry gas (Ca) 5. 5 5.0 4. 5 Distillate (04+) 30.9 84.6 84.3 ddltlonalpoklpg @1115 w Gained out employ Coke 13,6 10,4 m7 e a atmospheric residuum lroin West Texas Inspection of distillate:

GMVHYOAPI 1&5 28' 4 26 1 25,4 crude (16% on crude) into which two synthetic mum? pointy 78 92 90 5 sil ca-alumina gels, commonly used as catalysts gat 378 09 7 44 S 46 7 for cracking gas oil fractions were added. The

O Pour 0 80 60 65 results obtained with these additives is summa- Conredsml Carbon, rized in the following table in which the results wei ht percent 8.61 0.24 0.52 0.32 weight per. obtained without additives and with spent shale cent -L 0.94 0.68 0. e3 0. 7i Nitrogen, weight 2 09 1 46 1 48 1 44 fines 15 also included to facilitate comparison.

P9112811 Inspction on Table III Carbon, weight percent 8&3 M) I HYdrogn weight y Batch fire-Esteem coking under percent 3.1 a mospheric conditions Mag mum still temperature, 1,050 F.

Spentshalefinesburnedat1,l00 F toremoveburnable carbona- 23 7 ceous material (spent fines prior to burning contained 9.46% carbon (RD +l0#/gal. +l0#/ and 0.53% hydrogen). 3O 50) w +s giggil. ireillil)2% ireilliigfil,

Coking in the presence of fines resulted in an 52 mg Slalc sinc silica improvm'ent of around 4 weight percent of reg f zgif coverable o'il primarily at the expense of coke 7 formation. The employment of burned spent y i t percent shale fines offers only a slight yield improvement 011011 charged:

W a Dry gas(Cs) 5.3 9.1 6.9 8.6

over raw spent fines. Coking n the presence or D 5t111ate(O 74.1 75.7 67.0 67.3

spent shale fines does not result in any degradak Inspection of distiltion in product quality of the distillate over con- 1m (not corn for T R. L. E.):

ientional cok 4O gravity? API.-. io s 30.2 30.1 27.6 25.9

, our, 0 so so EXAMPLE 2 Sulfur, weight 00 A sample of 16% residuum nomwes Texas ;;g ;g;;- a1 50 crude (103 API gravity) was coined without g e e 0 0 21 7 additives and then under the same conditions but ss U vii 5365 MO MD in the presence of (a) spent Colorado shale fines, 45 F 43.8 40. 6 '54 42.0

(b) fine sand, (0) silica gel, (11) bauxite and (e) I reburnedspent shalefines. The following table Comparison of the results obtained with shale presents data from the above coking operations fines with the results obtained with the synthetic along with results from coking the residuum with silica-alumina catalytic solids, indicates a liquid no additives present. yield advantage of approximately 9 per cent for Table II Batch fire and steam coking of the 16% residuum under atmospheric conditions Maximum still temperature, 1,050 F. 16% Rfesidue rom r +10#/gal. war. With out gfiiffi gf i "git 51 +l0#/gal. j g fl g reburhed crude additives .sand 9 spent shale shale shale fines 0 (thru 200. (20/60 7 h 1 fines a fines b fines b mesh) mesh f g Yield, weight percent on oil charged: H

Dr'ygasiCs- 5.3 Distillate (04- 100.0 74.1

, Coke 20.6

Inspection of distillate:

Gravity, API l0. 3 30. 2 Aniline point, F 17 Sulfur, weight percent; 1. :7 Pour, F 65 Say. vis. at 100 F 43. 8 Conradson carbon, weight percent 1o. 0 0. 21

Inspection of coke:

Carbon, weight percent 88. 17 Hydrogen, weight percen 3. 07

e Spent shale fines l'r'om fluid retortiiig of Colorado oil shale in asingle vessel pilot unit.

11 Spent shale fines from fluid retorting of Colorado oil shale in a two vessel pilot unit.

Sand employed incokin'g Was mesh and finer.

Rebur'iied product from previous operations employing spent shale fines.

the shale fines. This shows the specific character of the catalytic effect of spent shale fines in the coking of liquid to semi-liquid carbonaceous materials or residual stocks.

The foregoing description contains a limited number of embodiments of the present invention. It will be understood that numerous variations are possible without departing from the scope of the following claims.

What is claimed and desired to be secured by Letters Patent is:

1. The method which comprises mixing shale oil containing a substantial portion boiling above 700 F. with spent unburnt Colorado oil shale fines containing up to 12% of burnable carbonaceous material and having a particle size distribution range substantially below 40 microns, in a ratio of 2 to 20 pounds of the spent shale fines per gallon of the oil, and coking the resulting mixture at coking temperatures between about 700 and 1100 F. to drive off distillate oil and convert the residue to coke.

2. A method according to claim 2 wherein the REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,467,758 Day Sept. 11, 1923 1,773,839 Zieley et a1 Aug. 26, 1930 1,945,530 Garrick Feb. 6, 1934 2,284,581 Kuhl May 26, 1942 2,423,674 Agren July 8, 1947 2,487,788 Buchan Nov. 15, 1949 2,489,702 Coast Nov. 29, 1949 

1. THE METHOD WHICH COMPRISES MIXING SHALE OIL CONTAINING A SUBSTANTIAL PORTION BOILING ABOVE 700* F. WITH SPENT UNBURNT COLORADO OIL SHALE FINES CONTAINING UP TO 12% OF BURNABLE CARBONACEOUS MATERIAL AND HAVING A PARTICLE SIZE DISTRIBUTION RANGE SUBSTANTIALLY BELOW 40 MICRONS, IN A RATIO OF 2 TO 20 POUNDS OF THE SPENT SHALE FINES PER GALLONN OF THE OIL, AND COKING THE RESULTING MIXTURE AT COKING TEMPERATURES BETWEEN ABOUT 700 AND 1100* F. TO DRIVE OFF DISTILLATE OIL AND CONVERT THE RESIDUE TO COKE. 